Method for forming deposited film

ABSTRACT

A method for forming a deposited film by introducing a gaseous starting material for formation of a deposited film and a gaseous halogenic oxidizing agent having the property of oxidation action on said starting material separately from each other into a reaction space to form a deposited film according to a chemical reaction, which comprises activating previously a gaseous substance (D) for formation of a valence electron controller in an activation space to form an activated species and introducing said activated species into the reaction space to form a doped deposited film.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a method for formation of a functional film, particularly a semiconductive deposited film which is can be used in a semiconductor device, photosensitive device for electrophotography, electronic device such as optical input sensor device for optical image inputting device, etc.

2. Related Background Art

Hitherto, for functional films, especially amorphous or polycrystalline semiconductive films, individually suitable film forming methods have been employed from the standpoint of desired physical characteristics, uses, etc.

For example, for formation of silicon type deposited films such as amorphous or polycrystalline non-single crystalline silicon which are optionally compensated for lone pair electrons with a compensating agent such as hydrogen atoms (H) or halogen atoms (X), etc., (hereinafter abbreviated as "NON-Si (H,X)", particularly "A-Si (H,X)" when indicating an amorphous silicon and "poly-Si (H,X)" when indicating a polycrystalline silicon) (the so-called microcrystalline silicon is included within the category of A-Si (H,X) as a matter of course), there have been attempted the vacuum vapor deposition method, the plasma CVD method, the thermal CVD method, the reactive sputtering method, the ion plating method, the optical CVD method, etc. Generally, the plasma CVD method has been widely used and industrialized.

However, the reaction process in formation of a silicon deposited film according to the plasma CVD method which has been generalized up to now is considerably complicated as compared with the conventional CVD method, and its reaction mechanism is not well understood. Also, there are a large number of parameters for formation of a deposited film (for example, substrate temperature, flow rate and flow rate ratio of the introduced gases, pressure during formation, high frequency power, electrode structure, structure of the reaction vessel, speed of evacuation, plasma generating system, etc.). Because of the combination of such a large number of parameters, the plasma may sometimes become unstable state, whereby marked deleterious influences were frequently exerted on the deposited film formed. Besides, the characteristic parameters must be selected for each device and therefore under the present situation it has been difficult to generalize the production conditions.

On the other hand, for the silicon type deposited film to exhibit sufficiently satisfactory electric and optical characteristics for respective uses, it is now accepted that the best to form it according to the plasma CVD method.

However, depending on the application use of the silicon type deposited film, bulk production with reproducibility must be attempted with full satisfaction of enlargement of area, uniformity of film thickness as well as uniformity of film quality, and therefore in formation of a silicon type deposited film according to the plasma CVD method, enormous installation investment is required for a bulk production device and also management for such bulk production becomes complicated, with management tolerance being narrow, and the control of the device being complex. These are pointed out as the problems to be improved in the future.

Also, in the case of the plasma CVD method, since plasma is directly generated by high frequency or microwave, etc., in the film forming space in which a substrate on which film is formed is arranged, electrons or a number of ion species generated may give damages to the film in the film forming process resulting in lowering of film quality or non-uniformization of film quality.

As an improvement of this point, the indirect plasma CVD method has been proposed.

The indirect plasma CVD method has elaborated to use the principal substance for formation of deposited film by forming an activated species of the principal substance for formation of deposited film by microwave, etc., at an upstream position apart from the film forming space and transporting said activated species to the film forming space.

However, even by such a plasma CVD method, transport of activated species is essentially required and therefore the activated species effective for film formation must have long life, whereby kinds of gases which can be employed are substantially limited, thus failing to provide various deposited films. Also, enormous energy is required for generation of plasma, and generation of the chemical species effective for film formation and their amounts cannot be essentially placed under simple management. Thus, vairous problems remain to be solved.

As contrasted to the plasma CVD method, the optical CVD method is advantageous in that no ion species or electrons are generated which cause damage to the film quality during film formation. However, there are problems when the light source does not include wave lengths tending toward the UV range, that a large scale light source and its power source are required in the case of industrialization, that the window for permitting the light from the light source to be introduced into the film forming space is coated with a film during film formation to result in lowering in dose during film formation, which may further lead to shut-down of the light from the light source into the film forming space.

As described above, in formation of silicon type deposited film, the points to be solved still remain, and it has been earnestly desired to develop a method for forming a deposited film which is capable of bulk production by attempting to save energy by means of a device of low cost, while maintaining the characteristics as well as uniformity which are practicably available. Especially, the above points are highly demanded when forming a semiconductor film of the p, n or i conduction type while enhancing the doping rate therein. These are also applicable in the case of enhancing the doping rate in other functional films, for example, semiconductive films such as silicon type films including silicon nitride films, silicon carbide films, silicon oxide films or germanium type films as the similar problems which should be solved respectively.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel method for forming a deposited film by removing the drawbacks of the method for forming deposited films as described above and at the same time without use of the formation method of the prior art.

Another object of the present invention is to provide a method for forming a deposited film which saves energy and at the same time is capable of producing a deposited film doped with a valence electron controller with uniform characteristics over a large area, and with easy management of film quality.

Still another object of the present invention is to provide a method for forming a deposited film by which a film excellent in productivity and bulk productivity, having high quality as well as excellent physical characteristics such as electrical, optical, and semiconductor characteristics can be easily obtained.

The method for forming a deposited film of the present invention which can accomplish the above objects is a method for forming a deposited film by introducing a gaseous starting material for formation of a deposited film and a gaseous halogenic oxidizing agent having the property of oxidation action on said starting material separately from each other into a reaction space to form a deposited film according to a chemical reaction, which comprises activating previously a gaseous substance (D) for formation of a valence electron controller in an activation space to form an activated species and introducing said activated species into the reaction space to form a doped deposited film.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a schematic illustration of a film forming device used in Examples of the present invention.

FIG. 2 and FIG. 3 are schematic illustrations of the activation devices used in Examples of the present invention.

FIG. 4 is a schematic illustration of a thin film transistor used in the Example of the present invention.

FIG. 5 is a schematic illustration of a solar battery used in the Example of the present invention.

FIG. 6 is a schematic illustration of an image forming member for electrophotography used in the Example of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

According to the method for forming a deposited film of the present invention, simplification of management and bulk production can be effected with full satisfaction of enlargement of area, uniformity of film thickness, and uniformity of film quality simultaneously with saving energy, without requiring enormous installation investment for bulk production apparatus, and also the management items for its bulk production become clear to afford broad width of management tolerance and simple adjustment of the device.

In the method for forming a deposited film of the present invention, the gaseous starting material to be used for formation of a deposited film and the gaseous substance (D) containing a component for a valence electron controller as the constituent can be previously activated in an activation chamber by discharging, light, heat energy, etc., and may be either capable of undergoing chemical reaction with a gaseous halogenic oxidizing agent or not. The gaseous substance (D) can be selected suitably as desired depending on the kind, the characteristic, use, etc., of the desired deposited film.

When the starting material for formation of a deposited film and the halogenic oxidizing agent are liquid or solid under ordinary state, they are introduced in gaseous state into the reaction space by performing bubbling with the use of a carrier gas such as Ar, He, N₂, H₂, etc., which can be done optionally with the application of heat.

When the gaseous substance (D) is liquid or solid under ordinary state, the substance (D) is made gaseous by performing bubbling with the use of carrier gas such as Ar, He, H₂, etc., which can be done optionally with the application of heat. The gaseous substance (D) is previously induced into the activation space and activated with discharging, light, heat energy, etc., followed by the introduction of the activated gaseous substance (D) (in the present specification, this is also referred to "activated species") and/or activated species (DA) generated from the gaseous substance (D) subjected to an activation treatment into the reaction space.

During this operation, the partial pressures and mixing ratio of the activated gaseous substance (D) and/or the activated species (DA) generated from the gaseous substance (D), the above gaseous starting material, and the gaseous halogenic oxidizing agent in the reaction space may be set by controlling the flow rate of the carrier gas and the vapor pressures of the gaseous starting material for formation of the deposited film and the gaseous halogenic oxidizing agent.

As the starting material for formation of a deposited film to be used in the present invention, for example, if tetrahederal type deposited films such as semiconductive or electrically insulating silicon type deposited films or germanium type deposited films, etc., are desired to be obtained, straight chain and branched chain silane compounds, cyclic silane compounds, chain germanium compounds, etc., may be employed as effective ones.

Specifically, examples of straight chain silane compounds may include Si_(n) H_(2n+2) (n=1, 2, 3, 4, 5, 6, 7, 8), examples of branched chain silane compounds include SiH₃ SiH(SiH₃)SiH₂ SiH₃, and examples of chain germanium compounds include Ge_(m) H_(2m+2) (m=1, 2, 3, 4, 5), etc. Otherwise, for example, if deposited films of tin are desired to be prepared, hydrogenated tin such as SnH₄. etc., may be employed as effective starting material.

Of course, these silicon type compounds and germanium type compounds may be used either as a single kind or as a mixture of two or more kinds.

The halogenic oxidizing agent to be used in the present invention is made gaseous when introduced into the reaction space and at the same time has the property of effectively oxidizing the gaseous starting material for formation of a deposited film introduced into the reaction space by mere chemical contact therewith, including halogenic gas such as F₂, Cl₂, Br₂, I₂, etc., and fluorine, chlorine, bromine, etc., under nascent state as effective ones.

These halogenic oxidizing agents are introduced into the reaction space under gaseous state together with the activated gaseous substance (D) and/or the activated species (DA) generated from the gaseous substance (D), and the gas of the starting material for formation of a deposited film as described above with desired flow rate and feeding pressure are given, wherein they are mixed with and the halogenic oxidizing agents are collided against the activated substance (D), the activated species (DA), and the above starting material to chemically react therewith, thereby oxidizing said activated substance (D), the activated species (DA), and the above starting material to generate efficiently plural kinds of precursors containing precursors under excited state. Of the precursors under excited state and other precursors generated, at least one of them functions as the feeding source for the constituent element of the deposited film formed.

The precursors generated may undergo decomposition or reaction to be converted to other precursors in an excited state or to precursors in another excited state, or alternatively in their original forms, if desired, although releasing energy to contact the substrate surface arranged in a film forming space, whereby a deposited film having a three-dimensional network structure is prepared.

As the energy level to be excited, it is preferable that the precursor in the above excited state should be subject to energy transition to a lower energy level, or alternatively it should be at an energy level accompanied with luminescence in the process of changing to another chemical species. By formation of an activated precursor including the precursor under excited state accompanied with luminescence in such a transition of energy, the deposited film forming process of the present invention proceeds with better efficiency and save energy to form a deposited film having uniform and better physical characteristics over the whole film surface.

As the material (D) to be used in the present invention, in the case of a silicon type semiconductor film and a germanium type semiconductor film, there may be employed compounds containing the p type valence electron controller, which functions as the so-called p type impurity, namely an element in the group IIIA of the periodic table such as B, Al, Ga, In, Tl, etc., and the n type valence electron controller which functions as the so-called n type impurity, namely an element in the group VA of the periodic table such as N, P, As, Sb, Bi, etc.

Specific examples may include NH₃, HN₃, N₂ H₅ N₃, N₂ H₄, NH₄ N₃, PH₃, P₂ H₄, AsH₃, SbH₃, BiH₃, B₂ H₆, B₄ H₁₀, B₅ H₉, B₅ H₁₁, B₆ H₁₀, B₆ H₁₂, Al(CH₃)₃, Al(C₂ H₅)₃, Ga(CH₃)₃, In(CH₃)₃, etc., as effective ones.

For introducing the gas of the above substance (D) into the activation space, it can be introduced from a plural number of independent gas feeding sources.

In the present invention, so that the deposit film forming process may proceed smoothly to form a film of high quality and having desired physical characteristics, the film forming factors include, the kinds and combination of the starting material for formation of a deposited film, the activated gaseous substance (D) or the activated species (DA) generated from the gaseous substance (D), and the halogenic oxidizing agent, mixing ratio of these, pressure during mixing, flow rate, the inner pressure in the film forming space, the flow types of the gases, and the film forming temperature (substrate temperature and atmosphere temperature) all of which should be suitably selected as desired. These film forming factors are organically related to each other, and they are not determined individually but determined respectively based upon mutual relationships. In the present invention, the ratio of the gaseous starting material for formation of a deposited film and the gaseous halogenic oxidizing agent introduced into the reaction space may be determined suitably as determined in relationship of the film forming factors related among the film forming factors as mentioned above. It is preferably 1/20 to 100/1, more preferably 1/10-50/1 in terms of flow rate ratio introduced.

The introduction proportion of the activated gaseous substance (D) or the activated species (DA) obtained by the activation of the gaseous substance (D) in the activation space into the reaction space may be set suitably as desired depending on the kind of the above gaseous starting material and the desired semiconductor characteristics of the deposited film to be prepared. It is preferably 1/1000000 to 1/10, more preferably 1/100000 to 1/20, optimally 1/100000 to 1/50 based on the above gaseous starting material.

The pressure during mixing when introduced into the reaction space may be preferably higher in order to enhance the chemical contact among the above gaseous starting material, the activated gaseous substance (D) and/or the activated species (DA), and the above gaseous halogenic oxidizing agent in probability. It is better to determine the optimum value suitably desired in view of the reactivity. Although the pressure during mixing may be determined as described above, each of the pressure during introduction may be preferably 1×10⁻⁷ atm to 10 atm, more preferably 1×10⁻⁶ atm to 3 atm.

The pressure within the film forming space, namely the pressure in the space in which the substrate on which surfaces is effected film formation is arranged if desired so that the precursors (E) under excited stated state generated in the reaction space and sometimes the precursors (F) formed as secondary products from said precursors (E) and may contribute effectively to film formation.

The inner pressure in the film forming space, when the film forming space is continuous openly to the reaction space, can be controlled in relationship to the introduction pressures and flow rates in the reaction space of the gaseous starting material for formation of a deposited film, said substance (D), and a gaseous halogenic oxidizing agent, for example, by application of a contrivance such as differencial evacuation or use of a large scale evacuating device.

Alternatively, when the conductance at the connecting portion between the reaction space and the film forming space is small, the pressure in the film forming space can be controlled by providing an appropriate evacuating device in the film forming space and controlling the evacuation amount of said device.

On the other hand, when the reaction space and the film forming space is integrally made and the reaction position and the film forming position are only spatially different, it is possible to effect differential evacuation or provide a large scale evacuating device having sufficient evacuating capacity as described above.

As described above, the pressure in the film forming space may be determined in the relationship with the introduction pressures of the gaseous starting material, said activated gaseous substance (D), the activated species (DA), and the gaseous halogenic oxidizing agent introduced into the reaction space. It is preferably 0.001 Torr to 100 Torr, more preferably 0.01 Torr to 30 Torr, optimally 0.05 to 10 Torr.

Further, the pressure in the activation space is intimately related with the pressure in the reaction space and it should desirably be higher than the inner pressure in the reaction space.

As for the flow type of the gases, it is necessary to design the flow type in view of the geometric arrangement of the gas introducing inlet, the substrate, and the gas evacuating outlet so that the starting material for formation of a deposited film, the activated gaseous substance (D) and/or the activated species (DA), and the halogenic oxidizing agent may be efficiently mixed during introduction of these into the reaction space, the above precursors (E) may be efficiently generated, and film formation may be adequately carried out without trouble. A preferable example of the geometric arrangement is shown in FIG. 1.

As the substrate temperature (Ts) during film formation, it can be set suitably as individually desired depending on the gas species employed, and the kind and required characteristics of the deposited film formed. In the case of obtaining an amorphous film, it is preferably from room temperature to 450° C., more preferably from 50° to 400 ° C. Particularly, in the case of forming a silicon type deposited film with better semiconductor characteristics and photoconductive characteristics, etc., the substrate temperature (Ts) should desirably be made 70° to 350 ° C. On the other hand, in the case obtaining a polycrystalline film, it should preferably be 200° to 650° C., more preferably 300° to 600° C.

As the atmosphere temperature (Tat) in the film forming space, it may be determined suitably as desired in relationship with the substrate temperature so that the above precursors (E) generated and the above precursors (F) are not changed to unsuitable chemical species for film formation, and also the above precursors (E) may be efficiently generated.

The substrate to be used in the present invention may be either electroconductive or electrically insulating, provided that it is selected as desired depending on the use of the deposited film formed. As the electroconductive substrate, there may be mentioned metals such as NiCr, stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, etc. or alloys thereof.

As insulating substrates, there may be conventionally used films or sheets of synthetic resins, including polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., glasses, ceramics, papers, and so on. At least one side surface of these insulating substrates is preferably subjected to treatment for imparting electroconductivity, and it is desirable to provide other layers on the side to which said electroconductive treatment has been applied.

For example, electroconductive treatment of glass can be effected by providing a thin film of NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In₂ O₃, SnO₂, ITO (In₂ O₃ +SnO₂) or the like thereon. Alternatively, a synthetic resin film such as polyester film can be subjected to the electroconductive treatment on its surface by vacuum vapor deposition, electronbeam deposition or sputtering of a metal such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc., or by laminating treatment with said metal, thereby imparting electroconductivity to the surface. The substrate may be shaped in any form such as cylinders, belts, plates or others, and its form may be determined as desired.

The substrate should be preferably selected from among those set forth above in view of adhesion and reactivity between the substrate and the film. Further, if the difference in thermal expansion between both is great, a large amount of strain may be created within the film to give a film without good quality, and therefore it is preferable to use a substrate so that the difference in thermal expansion between both is small.

Also, the surface state of the substrate is directly related to the structure of the film (orientation) or generation of a stylet structures, and therefore it is desirable to treat the surface of the substrate so that a film structure and a film texture which give desired characteristics may be obtained.

FIG. 1 shows an example of a preferable device for practicing the method for forming a deposited film of the present invention.

The deposited film forming device shown in FIG. 1 is broadly classified into the four components a main device, an evacuation system, a gas feeding system, and an activation chamber for valence controller.

In the main device, a reaction space and a film forming space are provided.

101-108, 126, and 127 are respectively bombs filled with the gases to be used for film formation, 101a-108a, 126a, and 127a are respectively gas feeding pipes, 101b-108b, 126b, and 127b are respectively mass flow controllers for controlling the flow rates of the gases from the respective bombs, 101c-108c, 126c, and 127c are respectively gas pressure gauges, 101d-108d, 126d, 127d, 101e-108e, 126e, and 127e are respectively valves, and 101f-108f, 126f, and 127f are respectively pressure gauges indicating the pressures in the corresponding gas bombs.

128 is an activation chamber, 129 and 130 are electrodes, 131 is a high frequency power source, 132 an activated species feeding pipeline, and 133 an activated species introducing pipe. 120 is a vacuum chamber equipped at the upper portion with a pipeline for gas introduction, having a structure for formation of the reaction space downstream of the pipeline, and also having a structure for formation of a film forming space in which a substrate holder 112 is provided so that a substrate 118 may be provided as opposed to the gas discharging outlet of said pipeline. The pipeline for gas introduction has a quadruple concentric arrangement structure, having from the innerside a first gas introducing pipe 109 for introducing the gases from the gas bombs 101 and 102, a second gas introducing pipe 110 for introducing the gases from the gas bombs 103-105, a third gas introducing pipe 111 for introducing the gases from the gas bombs 106-108, and an introducing pipe 133 for introducing the activated species activated in the activation chamber 128.

For gas discharging to the reaction space of each gas introducing pipe, each position is designed so as to be arranged at a position further from the surface position of the substrate as the pipe is nearer to the inner side. In other words, the gas introducing pipes are arranged so that the pipe on the outer side may enclose the pipe existing within the innerside thereof.

The gases from the respective bombs are fed into the respective introducing pipes through the gas feeding pipelines 123-125, respectively. The activated species are fed through the activated species feeding pipeline 132 into the activated species introducing pipe 133.

The respective gas introducing pipes, the respective gas feeding pipe lines, and the vacuum chamber 120 are evacuated to vacuum through the main vacuum valve 119 by means of a vacuum evacuating device not shown.

The substrate 118 is set at a suitable desired distance from the positions of the respective gas introducing pipes by moving vertically the substrate holder 112.

In the case of the present invention, the distance between the substrate and the gas discharging outlet of the gas introducing pipe may be determined appropriately in view of the kinds and the desired characteristics of the deposited film formed, the gas flow rates, the inner pressure in the vacuum chamber, etc. It is preferably several mm to 20 cm, more preferably 5 mm to about 15 cm.

113 is a heater for heating the substrate which is provided in order to heat the substrate to an appropriate temperature during film formation, to preheat the substrate 118 before film formation, or further to anneal the film after film formation.

The substrate heating heater 113 is supplied with power through a conductive wire 114 from a power source 115.

116 is a thermocouple for measuring the substrate temperature (Ts) and is electrically connected to the temperature display device 117.

The present invention is described in more detail by referring to the following Examples.

EXAMPLE 1

By use of the film forming device shown in FIG. 1, a thin film transistor (hereinafter called "TFT") as shown in FIG. 4 was prepared according to the method for formation of deposited film of the present invention.

The above TFT was constituted of 7059 glass (produced by Corning Co.) 434, an amorphous silicon layer (first layer thickness 7000 Å) 433, an amorphous silicon layer doped with phosphorus to a high concentration (second layer thickness 500 Å) 432, a silicon oxide layer (third layer thickness 1000 Å) 431, and an aluminum electrode 429.

In this Example, on deposition of the amorphous silicon layer (second layer) doped with phosphorus to a high concentration, in the activation chamber 128 shown in FIG. 1, after the valence electron controller PH₃ was activated by RF glow discharge, the activated species formed from PH₃ was introduced into the deposition chamber 120 through the introducing pipe 133 to deposit an amorphous silicon layer (second layer) doped with phosphorus to a high concentration. As to other conditions, semiconductor layers and insulating layers necessary for TFT were prepared under the conditions shown in Table 1.

The film thickness of each sample was measured with a layer thickness measuring apparatus of Alpha-Step (manufactured by TENCOR Co.).

The TFT of the present Example exhibited an on-off ratio improved by 10% in comparison with that prepared by PCVD method above.

EXAMPLE 2

In the deposited film forming device shown in FIG. 1, the high frequency power source 131 connected to the activation chamber 128 was replaced with a microwave power source, and a solar battery as shown in FIG. 5 was prepared according to the method for formation of deposited film of the present invention.

The above solar battery was constituted of a glass No. 7059 (produced by Corning Co.) 500 having transparent electrodes vapor deposited thereon, a p-type semiconductor layer (first layer thickness 500 Å) 501, an i-type semiconductor layer (second layer thickness 1 μm) 502, an n-type semiconductor layer (third layer thickness 500 Å) 503, and an aluminum electrode 504.

The layer thicknesses were measured in the same manner as in Example 1.

During formation of the first layer and the third layer, after the valence electron controlling agent B₂ H₆ or PH₃ was activated in the activation chamber 128, the activated species was introduced through the introducing pipe 133 into the deposited film forming chamber 120 to form the first layer and the third layer of p-type or n-type therein. As to other conditions, semiconductor layers necessary for solar battery were formed under the conditions shown in Table 2.

The solar battery thus obtained exhibited a conversion efficiency improved by 10% as compared with the solar battery prepared by PCVD method alone.

EXAMPLE 3

In the deposited film forming device shown in FIG. 1, the activation chamber 128 was exchanged with an activation device utilizing optical energy of excimer laser shown in FIG. 2.

The activation device shown in FIG. 2 is constituted of an activation chamber 201, an excimer laser 202, a window 205 for irradiation of excimer laser, and a gas feeding pipeline 203 connected to the gas feeding pipeline 134 in FIG. 1, and also a gas feeding line 204 connected to the gas feeding pipeline 132 in FIG. 1.

By utilizing the deposited film forming device having the activation device utilizing optical energy as described above, an image forming member for electrophotography as shown in FIG. 6 was prepared according to the method for forming deposited film of the present invention.

The above image forming member for electrophotography shown in FIG. 6 was constituted of an aluminum substrate 600, a charge injection impeding layer (first layer, amorphous silicon layer doped with B, 0.5 μm) 601, a photosensitive layer (second layer, amorphous silicon layer, 18 μm) 602, and a surface protective layer (third layer, amorphous silicon carbide layer, 0.5 μm) 603.

In this Example, on depositing an amorphous silicon layer doped with boron to a high concentration, in the activation chamber 201 shown in FIG. 2, after the valence electron controlling agent B₂ H₆ was activated, the activated species formed from B₂ H₆ was introduced through the gas introducing pipe 133 into the deposition chamber 120 to deposit an amorphous silicon layer (first layer) doped with boron to a high concentration.

The layer thickness were measured in the same manner as in Example 1.

Following otherwise the conditions as shown in Table 3, an image forming member for electrophotography was prepared.

The image forming member for electrophotography thus prepared exhibited a charging ability improved by 50% or more in comparison with that in which all layers were prepared by PCVD method alone.

EXAMPLE 4

In the deposited film forming device in FIG. 1, the activation chamber 128 was exchanged with an activation chamber having an electric furnace shown in FIG. 3.

The activation device shown in FIG. 3 is constituted of an activation chamber 301, an electric furnace 302, a gas feeding line 303 connected to the gas feeding pipeline 134 shown in FIG. 1 and a gas feeding line 304 connected to the gas feeding pipeline 132 shown in FIG. 1.

By utilizing the deposited film forming device having the activation chamber utilizing heat energy as described above, a solar battery shown in FIG. 5 was prepared according to the method for forming deposited film of the present invention.

The layer constitution of the solar batter of this Example was the same as in Example 2.

In this Example, during formation of the first layer and the third layer, the charge controlling agent PH₃ or B₂ H₆ was activated in the activation chamber 301 and then the activated species was introduced through the introducing pipe 133 into the deposited film forming chamber 120 to form an n-type or p-type first layer and third layer therein. Following otherwise the conditions shown in Table 4, semiconductor layers necessary for solar battery were formed.

The layer thickness were measured in the same manner as in Example 1.

The solar battery thus obtained exhibited a conversion efficiency improved by 12% as compared with the solar battery prepared by PCVD method alone.

As can be seen from the detailed description and the respective examples as set forth above, according to the deposited film forming method of the present invention, deposited films having uniform physical characteristics with good doping efficiency over a large area can be obtained with easy management of film quality at the same time as achievement of energy saving. Also, it is possible to easily obtain films with good bulk productivity, having a high quality of physical properties such as electrical, optical, and semiconductor properties, etc.

                  TABLE 1                                                          ______________________________________                                         Layer                           Acti-  Acti-                                   con-                            vation vation                                  stitution                                                                             Starting materials                                                                            Flow rate method energy                                  ______________________________________                                         First  SiH.sub.4      20         --    --                                      layer  F.sub.2 /He = 1/10                                                                            200                                                      Second SiH.sub.4      20        PH.sub.3 acti-                                                                        10 W                                    layer  F.sub.2 /He = 1/10                                                                            200       vated by                                              PH.sub.3 /He = 1000 ppm                                                                        2        RF glow                                        Third  SiH.sub.4      10         --    --                                      layer  F.sub.2 /He = 1/10                                                                            10                                                              O.sub.2 /He = 1/10                                                                            100                                                      ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         Layer                           Acti-  Acti-                                   con-                            vation vation                                  stitution                                                                             Starting materials                                                                            Flow rate method energy                                  ______________________________________                                         First  SiH.sub.4      20        B.sub.2 H.sub.6 ac-                                                                   50 W                                    layer  F.sub.2 /He = 1/10                                                                            200       tivated                                               B.sub.2 H.sub.6 /He = 1000 ppm                                                                 2        by glow                                                                        discharge                                                                      of micro-                                                                      wave                                           Second SiH.sub.4      20        --     --                                      layer  F.sub.2 /He = 1/10                                                                            200                                                      Third  SiH.sub.4      20        PH.sub.3 acti-                                                                        50 W                                    layer  F.sub.2 /He = 1/10                                                                            200       vated by                                              PH.sub.3 /He = 1000 ppm                                                                        2        glow dis-                                                                      charge of                                                                      micro-                                                                         wave                                           ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     Layer                            Activation                                    constitution                                                                         Starting materials                                                                        Flow rate                                                                            Activation method                                                                        energy                                        __________________________________________________________________________     First SiH.sub.4  20    B.sub.2 H.sub.6 activated                                                                Excimer laser                                 layer F.sub.2 /He = 1/10                                                                        200   by optical                                                                               20 W                                                B.sub.2 H.sub.6 /He = 1000 ppm                                                            20    energy                                                  Second                                                                               SiH.sub.4  20     --       --                                            layer F.sub.2 /He = 1/10                                                                        200                                                           Third SiH.sub.4  20     --       --                                            layer F.sub.2 /He = 1/10                                                                        200                                                                 CH.sub.4   20                                                            __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________     Layer                            Activation                                    constitution                                                                         Starting materials                                                                        Flow rate                                                                            Activation method                                                                        energy                                        __________________________________________________________________________     First SiH.sub.4  20    B.sub.2 H.sub.6 activated                                                                Heating at                                    layer F.sub.2 /He = 1/10                                                                        200   by heat   1000° C.                                     B.sub.2 H.sub.6 /He = 1000 ppm                                                             2    energy                                                  Second                                                                               SiH.sub.4  20     --        --                                           layer F.sub.2 /He = 1/10                                                                        200                                                           Third SiH.sub.4  20    PH.sub.3 activated                                                                       Heating at                                    layer F.sub.2 /He = 1/10                                                                        200   by heat   1000° C.                                     PH.sub.3 /He = 1000 ppm                                                                    2    energy                                                  __________________________________________________________________________ 

We claim:
 1. A method for forming a deposited film on a substrate by introducing into a reaction space a non-activated gaseous starting material for formation of the deposited film and a non-activated gaseous halogenic oxidizing agent selected from the group consisting of F₂, Cl₂, Br₂, and I₂ having the property of oxidation action on said non-activated gaseous starting material to form a deposited film by a direct chemical reaction between said non-activated gaseous starting material and said non-activated gaseous halogenic oxidizing agent, comprising:(a) activating a gaseous substance (D) which includes a component to act as a valence electron controller in an activation space separate from said reaction space to form an activated species; and (b) introducing said activated species into the reaction space so as to form a mixture with said non-activated gaseous starting material and said non-activated gaseous halogenic oxidizing agent and form a deposited film controlled in valence electron on said substrate without the use of external discharge energy in the reaction space.
 2. A method for forming a deposited film according to claim 1, wherein luminescence is accompanied during formation.
 3. A method for forming a deposited film according to claim 1, wherein said gaseous starting material is a chain silane compound.
 4. A method for forming a deposited film according to claim 3, wherein said chain silane compound is a straight chain silane compound.
 5. A method for forming a deposited film according to claim 4, wherein said straight chain silane compound is represented by the formula Si_(n) H_(2n+2) (n is an integer of 1 to 8).
 6. A method for forming a deposited film according to claim 3, wherein said chain silane compound is a branched chain silane compound.
 7. A method for forming a deposited film according to claim 1, wherein said gaseous starting material is a silane compound having a cyclic structure of silicon.
 8. A method for forming a deposited film according to claim 1, wherein said gaseous starting material is a chain germanium compound.
 9. A method for forming a deposited film according to claim 8, wherein said chain germanium compound is represented by the formula Ge_(m) H_(2m+2) (m is an integer of 1 to 5).
 10. A method for forming a deposited film according to claim 1, wherein said gaseous starting material is a hydrogenated tin compound.
 11. A method for forming a deposited film according to claim 1, wherein said gaseous starting material is a tetrahedral type compound.
 12. A method for forming a deposited film according to claim 1, wherein said gaseous halogenic oxidizing agent is selected from the group consisting of F₂, Cl₂, Br₂ and I₂.
 13. A method for forming a deposited film according to claim 1, wherein said gaseous halogenic oxidizing agent contains fluorine gas.
 14. A method for forming a deposited film according to claim 1, wherein said gaseous halogenic oxidizing agent contains chlorine gas.
 15. A method for forming a deposited film according to claim 1, wherein said gaseous halogenic oxidizing agent contains fluorine atoms as the constituents.
 16. A method for forming a deposited film according to claim 1, wherein said gaseous halogenic oxidizing agent contains a halogen under nascent state.
 17. A method for forming a deposited film according to claim 1, wherein said substrate is arranged at a position opposed to the direction in which said gaseous starting material and said gaseous halogenic oxidizing agent are introduced into said reaction space.
 18. A method for forming a deposited film according to claim 1, wherein said gaseous starting material and said gaseous halogenic oxidizing agent are introduced into said reaction space through a transporting pipe of a multi-tubular structure.
 19. A method for forming a deposited film according to claim 1, wherein said gaseous substance (D) contains an element in the group IIIA of the periodic table.
 20. A method for forming a deposited film according to claim 1, wherein said gaseous substance (D) is diborane (B₂ H₆) or boron fluoride (BF₃).
 21. A method for forming a deposited film according to claim 1, wherein said gaseous substance (D) contains an element in the group VA of the periodic table.
 22. A method for forming a deposited film according to claim 1, wherein said gaseous substance (D) is phosphine (PH₃), phosphorus pentafluoride (PF₅) or arsine (AsH₃).
 23. A method for forming a deposited film according to claim 1, wherein said gaseous substance (D) is diluted with at least one gas among H₂, He, Ne, Ar, Kr, Xe, and Rn before introduction into the activation space.
 24. A method for forming a deposited film according to claim 1, wherein discharging, light or heat energy is utilized as the activation method in said activation space. 